Mineral oil composition



Patented Apr. 29, 1947 MINERAL OIL COMPOSITION Thomas '1. Noland,Richmond, Ky., assignor to Soeony-Vacuum Oil Company, Incorporated, acorporation of New York No Drawing. Application January 18, 1945, SerialNo. 573,466

12 Claims.

This invention has to do with the stabilization of viscous mineral oilfractions against the deleterious effects of oxidation or deteriorationwith use by the addition thereto of oxidationinhibitors. Morespecifically, the invention is directed to the improvement of viscousmineral oil fractions by a combination of such inhibitors; namely, aprimary oxidation inhibitor and a secondary inhibitor which when admixedwith a viscous mineral oil in minor proportions will prevent or delaycertain other undesirable changes taking place in the oil.

As is well known to those familiar with the art, substantially all ofthe numerous fractions obtained from mineral oils and refined for theirvarious uses are susceptible to oxidation. The susceptibility of an oilfraction to oxidation and the manner in which such oxidation manifestsitself within the oil varies with the type and degree of refinement towhich the oil has been subjected and with the conditions under which itis used or tested; that is, the products formed in an oil fraction as aresult of oxidation and the degree to which they are formed depends uponthe extent to which the various unstable constituents orconstituentswhich may act as oxidation catalysts have been removed byrefining operations and also upon the conditions of use to which the oilis put.

The present invention is predicated upon the discovery that theoxidation characteristics of viscous mineral oil fractions are greatlyimproved by the incorporation therein or minor proportions of each oftwo inhibitors which are designated herein as primary oxidationinhibitors and secondary inhibitors.

The primary oxidation inhibitors contemplated herein are stable,oil-soluble phosphorusand sulfur-containing reaction products obtainedby reaction of phosphorus penta-sulilde and a cycle stock characterizedby an olefin and an aromatic content of from about 3 per cent to about'7 per cent and from about 40 per cent to about 60 per cent,respectively, under the following interrelated reaction conditions:

1. Between about 1 per cent and about 8 per cent by weight of P285 basedupon the weight of said cycle stock,

2. A temperature between about 125 C, and about 200 C., and

3. A relatively short reaction time.

The hydrocarbon reactants are, as indicated above, cycle stockscontaining from about 3 per cent to about 7 per cent of olefins and fromabout 40 per cent to about per cent of aromatics, as determined by thefollowing test method:

Twenty-five milliliters of a solution containing per cent by weight ofsulfuric acid (sp. gr.. 1.84) and 30 per cent of P201; are placed in aglass stoppered sulfonation bottle (a modified Babcock bottle-A. S. I'.M. Standards on Petroleum Products and Lubricants, Sept. 1943, page381). The bottle is immersed in ice water for five minutes; then 10milliliters of the hydrocarbon are added. The bottle is shaken for 10minutes while cooling with ice water. Sulfuric acid (sp. gr., 1.84) isadded until the top meniscus of the hydrocarbon layer is brought up tothe 100 per cent mark on the graduated portion of the neck. The bottleis then stoppered and is centrifuged for 10 minutes. The milliliters ofhydrocarbon oil layer remaining are read and this value is subtractedfrom the original 10 milliliters to obtain the combined amounts ofarcmatic and olefin contents of the sample. By repeating the sameprocedure, except for using per cent sulfuric acid instead of theH:SO4P:O mixture, the olefinic content of the sample is obtained. Thusolefinic content subtracted from the combined olefin and aromaticcontent gives the amount of aromatic material present.

Preferably, the hydrocarbon reactants are also characterized by thefollowing: boiling range from about C. to about 400 0., and specificgravity from about 0.88 to about 0.93. In general, such cycle stocks areobtained from thermal cracking operations of crude oils, but otherstocks characterized as above may also be used. Typical of such otherstocks are light gas oils, such as a light gas oil containing 4 per centoleflns and 46 per cent aromatics, a specific gravity of 0.8833 and aboiling range from C. to 380 C. For this reason, the hydrocarbonreactants may be broadly considered as hydrocarbon stocks characterizedby the aforesaid percentages of olefins and aromatics.

The amount of P285 reacted with the cycle stocks contemplated herein isan important consideration. Stable, oil-soluble reaction productscontaining appreciable quantities of phosphorus and sulfur are obtainedwhen the amount of P255 so reacted is from about 1 per cent to about 8per cent by weight of the hydrocarbon reactant. Particularly preferredreaction products, however, are obtained with about 5 per cent by weightof P285. When amounts of the order of 10 per cent and 15 per cent ofP285 are used, it has been found that the phosphorusandsulfur-containing reaction products obtained therewith are unstable whenheated and are oil-insoluble. As used herein the term "011 soluble" isdescriptive of those reaction products which are soluble in oil inamounts of at least 1 per cent by weight.

Another important consideration in the prepuct--product B-contained 1.26per cent phosphorus and 3.6 per cent sulfur.

EXAMPLE 3 Five hundred grams of product B obtained in aration of theaforesaid reaction products is reac- 5 Example 2 were vacuum dlstmied toa maximum tion time. In general, superior reaction products. temperatureof 172? 3 Order to remove in quantities Such as shown in the followingunreacted recycle stock therefrom. The residueamples. are obtained whenthe reaction time is product ccontamed per cent Phosphorus relativelyshort. such as from about 2 hours to and per cent 511mm about 8 hours.While reaction times as long as Reaction product? obtamed from recyclestock about 12 hours have been used and satisfactory and Prepared as PExample 2 above are shown reaction products obtained therewith. reactionTable I below m order to demntrate the times in the neighborhood of 4hours are influence of each of the several react1on variaferred. It isto be understood, however, that the 15 mes-um?" temperature andconcentration of reaction time may be varied considerably depend- P255The copper Strip tests referred to m the ing upon the quantities ofreactants and the rem were made by immersing a P0115119: copper actiontemperatures used in the preparation of F in a 1 cent blend of aroeactmn product said reaction products in 011 and heating the blend at100 C. for 24 hours. The interrelation of the foregoing reaction Thecopper F .F the plesence or absence of free 01 active sulfur whichcorrodes factors willbc apparent from the following typical copper Anasterisk H has been used in the examples recited below, and also thoseset forth table wherever the copper strip used in the copper m Tablestrip test was not corroded in each test; that the EXAMPLE 1 5 reactionproduct was stable; and that the reaction A reaction stock-recycle stockA-from a ther- 2 product was soluble in oil.

Table I P cent Composition p" ,up Product (by at) i?" 5g lg Percent s aStability Solubility E. s 100-200 4 1.23 as F 5 4 Unstable. Insoluble.

:22 .2 ii I I I Conceal 1 I I mal liquid phase cracking operation andhaving It will bqapparent from the data tabulated in the followingcharacteristics, was used: 45 TableI above that reaction temperatures inexcess of 200 C, are unsatisfactory. The desired reac- 212?.321252:;5::jjjlf ji iSET: tion products as indicated in Table I arethose Specific gravity 03939 prepared under the reaction conditionsdefined Aniline number 105.5 heremabove' Boiling range (0); Anothercycle stock which was also found to Initial 3 Pt 97 be particularlydesirable was a cycle stock. obm cent 230 tained from a Cross still, andcharacterized by 50 do 274 the following: do- 32'? Olefin content percent 5 End point 366 Aromatic content do- 57 Recovery per cent.-- 98.5Specific gravity 0.9236 Aniline number 80 One thousand grams of recyclestock A was reacted, with stirring, with '70 grams or P235 at Bomngrange -370 180 C. for 8 hours. The reaction mixture thus While productsA, B and C, shown above in obtained was diluted with naphtha 1 boilingrange (30 E a p s 1 through and Products E, G, H 88-135" C.) washed with20 per cent Nags soluand I shown in Table I are particularly desirabletion. water washed, filtered and the fill rate heated for use inpetroleum f a t r a ed 113 11 to c. at 10 mm. pre sure to remove the p sp p ed nasimi r m nn r f om o h r naphtha. The reaction productcontained 1.19 hydrocarbon reactants are undesirable or such per centphosphorus and 3.06 per cent sulfur, and 05 use. The data pres nted iTable II b low is illusis identified hereinafter s product A, trative oftheir undesirable character. The cop- EXAMPLE 2 per strip tests referredto in this table were obtained in the manner described in connection neth u and r m of r cycle l A w with Table I. The heat stability testsshown in ac with stirring. with 50 grams of 5 at 70 Table II were madeby heating a 1 per cent blend for 3 hours" The 1(faction mixture 50 of areaction product in oil at 100 C. for 24 hours. obtained was then co ledto 100 C.. 52.5 grams An asterisk has been used as in Table I to indi-(5 per cent by weiclitl of Aiiapuleus clay \vas cote that the copperstrip in the copper strip added thereto and the clay was subsequentlyrctests was not corroded in each test, and that the moved thereirom byfiltering. The r action prod- 76 f ti n product was stable to heat.

Table II Composi- P t tion Prod- Temp. Temp. Co per Strip HeatHydmcarbo" uct g fl Q o. hours Per wst Stability Rema'ks cent cent P SCatelytically Cracked Cycle M 190-195 434 0.88 2.1 Corrosive black Poor:sludge Sludge formed durin Stock: strip deposited reaction: additionsPer cent Olefin, 3 oil-insoluble sludge Per cent Aromatic, 35 generatedon standg. castalyically Cracked Cycle N 5 190-195 4% 1.04 2.0 do do Do.

toc

Percent Olefin, 1 Per cent Aromatic, 35 No. 2 Fuel Oil from Catalytic O5 80-200 2% do Unstable Do.

CrackingO ration:

Per amt lefln,0 Per cent Aromatic, 36 i It will be apparent from theresults set foith in Table II above that the reaction products ofhydrocarbon reactants which are not characterized by the required olefinand aromatic contents defined above are greatly inferior to the relatedreaction products from the cycle stocks contemplated herein andillustrated in Examples 1 through 3 and in Table I. For example, it isapparent that the reaction products obtained from the catalytic cyclestocks and the No. 2 fuel oil defined in Table II are corrosive tocopper and are unstable when heated, being so unstable when heated thatconsiderable quantities of oil insoluble sludge are deposited therefrom.Thus, the latter reaction products have little or no value as additionagents for petroleum fractions, particularly viscous mineral oils. Onthe contrary, however, the reaction products contemplated herein are notcorrosive to copper and are stable when heated. It will be recognized,therefore, that the reaction products of this invention are much moremarketable in the oil industry and other industries than are the relatedreaction products of such hydrocarbon reactants as those shown above inTabl II.

When used in viscous mineral oil fractions in small amounts, theaforesaid primary oxidation inhibitors effect improvement of several ofthe oxidation characteristics thereof by preventing, for example,corrosion of hard metal bearings, by inhibition or acid-formation, byinhibition of formation of gummy deposits in engines, by preventingincrease in viscosity, etc. However on standing for several days or whenheated and then left to stand, an oil composition comprised only of aviscous mineral oil fraction and a primary oxidation inhibitor tends tobecome cloudy. This shortcoming has now been overcome by incorporatingin such oil composition a small amount of a secondary inhibitor.

The secondary inhibitors of this invention which are capable ofregulating or preventing the aforesaid haze problem are oil-misciblemetal salts of sulfonic acids. These sulfonic acids include both thoseprepared from aromatic hydrocarbons. or substituted aromatichydrocarbons, by treatment with strong sulfuric acid, olcum.chlorsulfonic acid, etc., and those obtained by treatment of varioupetroleum fractions with the same reagents. Any metallic salt of anyorganic sulfonic acid that is sufficiently soluble in petroleum oils iscontemplated by this invention as the secondary inhibitor. Among themetals which are especially suitable for this purpose are sodium,potassium, magnesium. calcium, cobalt, tin, strontium and barium.Particularly preferred are barium, sodium and calcium.

Of the sulfonic acids contemplated by the present invention, preferenceis given to the substituted aroma-tic sulfonic acids and to thepetroleum sulfonic acids. Both monoand polysubstituted aromatic sulfonicacids are contemplated, particular prcference being given to thealkyl-substituted benzene sulfonic acids. 01 the monoand poly-alkylsubstituents for the aromatic sulfonic acids, the so-called "wax"substituents-that is, those alkyl substituents containing at least about20 carbon atoms-are particularly preferred.

The praticularly-preferred compositions of primary and secondaryinhibitors in viscous mineral oil fractions which are contemplatedherein are those in which the primary inhibitor is 9. P255- cycle stockreaction product or a Pass-light gas oil reaction product, of the typedescribed above, and the secondary inhibitor is either barium or calciumdiwax benzene sulfonate, barium or calcium petroleum sulfonate, orsodium petroleum sulfonate.

As, stated above, oil compositions comprising only a viscous mineral oilfraction and a typical primary oxidation inhibitor have a tendency todevelop a haze, the formation of which can be suppressed by the additionto such compositions of a small amount of a secondary inhibitor. namely,an oil-miscible metal salt of a sulfonic acid. This fact is demonstratedby the test results set forth in table III below. The oil used in thesetests was a solvent-refined S. A. E. 10 grade motor oil.

The Pass-cycle stock reaction product (prodnot B) was prepared asdescribed in Example 2 above.

The barium diwax benzene sulfonate used as the haze-inhibitor was"prepared by reacting a 10 per cent chlor-paraffin wax with benzene toform a diwax benzene, which was treated with oleum to form the sulfonicacid, which in turn was neutralized with barium hydroxide. In order toreduce the viscosity and to increase the ease of handling, this productwas blended in a 1:1 ratio with an S. A. E, 30 grade motor oil. Theblend contained 5.17 per cent barium and 1.5 per cent sulfur.

The sodium petroleum sulfonate used in these tests was the sodium saltof an oil-soluble sulionic acid prepared by treating a Mid-Continent,distillate of seconds Saybolt Universal viscosity at F. with olcum. Itcontained 2.57 per cent sulfur.

The barium petroleum sulfonate was prepared from the above sodium saltby treatment with Each solution. It contained 6.9 per cent barium.

The variou blends indicated in Table III were placed in -ounce bottlesand kept at room temperature in diffused light for the length or timegiven below, with the following results:

8 and sulfur-containing reby reaction of phossoluble, phosphorusactionproduct obtained The results shown above in Table III demonstrateeffectively that haze-formation in an oil containing as a primaryoxidation inhibitor a PzSs-cycle stock reaction product is appreciablyinhibited by the addition of a small amount of the secondary inhibitorcontemplated by this invention.

The amount of secondary inhibitor necessary to effect the desiredhaze-inhibition depends upon the concentration of primary oxidationinhibitor in the oil as well as upon the type of mineral oil fractionused. In general, however, from about 1.0 to about 10.0 per cent byweight of the secondary inhibitor based upon the amount of primaryinhibitor present will be suilicient to effectively regulatehaze-formation. The amount of primary oxidation inhibitor contemplatedfor use in the oil compositions of the present invention is from about0.1 per cent to about 3.0 per cent, although about 0.1 per cent to about1 per cent of these reaction products will usually suflice. Accordingly,the amount of secondary inhibitor used in the oil blend will be fromabout 0.001 per cent to about 0.3 per cent by weight.

As contemplated herein, the primary and secondary inhibitors or thisinvention may be incorporated in a viscous mineral oil traction eitherby adding the secondary inhibitor to the primary inhibitor before bothare blended with the oil or by adding the secondary inhibitor separatelyto the blend of the oil and theprimary inhibitor. The term, "mineral oilcomposition, as used herein and as recited in all of the appendedclaims, is inclusive of all mineral oil fractions containing a primaryoxidation inhibitor and a secondary inhibitor and of all oilcompositions obtained or prepared by any of the proced ures hereinabovedescribed. Any oil compositions so obtained or prepared is substantiallyfree of haze normally occurring in an oil composition containing theprimary oxidation inhibitor alone.

It is also to be understood that the examples, procedures, and oilcompositions described herein are illustrative only and are not to beconstrued as limiting the scope of this invention thereto. Thus, allcycle stocks and light gas oils as defined above may be used in place ofthose shown in the foregoin examples; any metallic salt of any sulfonicacid that is sufliciently soluble in petroleum oils is suitable for useas the secondary inhibitor; and the mineral oils disclosed above are buttypical of all viscous mineral oil fractions which may be used in thisinvention.

I claim:

1. A mineral oil composition comprising a viscous mineral oil fractioncontaining a minor proportion, from about 0.1 per cent to about 3.0 percent, sufficient to inhibit the deteriorating effects of oxidation uponthe oil, of a stable, oilphorus penta-sulflde and a hydrocarbon stock ata temperature between about C. and about 200 C. for a relatively shortreaction time. said hydrocarbon stock being characterized by an olefincontent of from about 3 per cent to about 7 per cent and an aromaticcontent of from about 40 per cent to about 60 per cent, said phosphoruspenta-sulfide representing from about 1 per cent to about 8 per cent byweight of the said hydrocarbon stock, and the said reaction productnormally tending to form a haze in the oil; and a minor proportion, fromabout 0.001 per cent to about 0.3 per cent, suflicient to suppress theformation of said haze. of an oil-miscible metal salt of a sulfonicacid. I

2. A mineral oil composition comprising a viscous mineral oil fractioncontaining a minor proportion, from about 0.1 per cent to about 3.0 percent, sufficient to inhibit the deteriorating effects of oxidation uponthe oil. of a stable, oilsoluble, phosphorusand sulfurcontainingreaction product obtained by reaction of phosphorus penta-sulfide and alight gas oil at a temperature between about 125 C. and about" 200 C. 0:a relatively short reaction time, said light gas oil being characterizedby an olefin content of about 4 per cent and an aromatic content ofabout 46 per cent, said phosphorus penta-sulflde representing about 5per cent by weight of Said light gas oil. and the said reaction productnormally tending to form a haze in the oil; and a minor proportion, fromabout 0.001 per cent to about 0.3 per cent, suiliclent to suppress theformation of said haze, of an oil-miscible metal salt of a sulfonicacid.

3. A mineral oil composition comprising a viscous mineral oil fractioncontaining a minor proportion, from about 0.1 per cent to about 3.0 percent, suflicient to inhibit the deteriorating effects of oxidation uponthe oil, of a stable, oilsoluble, phosphorusand sulfur-containingreaction product obtained by reaction of phosphorus penta-sulfide and acycle stock at a temperature between about 125 C. and about 200 C. for arelatively short reaction time. said cycle stock being characterized byan olefin content of from about 3 per cent to about 7 per cent and anaromatic content of from about 40 per cent to about 60 per cent, saidphosphorus penta-sulfide representing from about 1 per cent to about 8per cent by weight of the said cycle stock, and the said reactionproduct normally tending to form a haze in the oil; and a minorproportion, from about 0.001 per cent to about 0.3 per cent. suflicientto suppress the formation of said haze. of an oil-miscible metal salt ofa sulionic acid.

4. A mineral oil composition comprising a viscous mineral oil fractioncontaining a minor proportion, from about 0.1 per cent to about 3.0 percent, sufficient to inhibit the deteriorating effects of oxidation uponthe oil. or a stable. oilsoluble, phosphorusand sulfur-containingreaction product obtained by reaction of phosphorus penta-sulflde and acycle stock at a temperature between about 125 C. and about 200 C. for areaction time from about 2 hours to about 8 hours, said cycle stockbeing characterized by an olefin content of from about 3 per cent toabout '1 per cent and an aromatic content of from about 40 per cent toabout 60 per cent, said phosphorus penta-sulfide representing from about1 per cent to about 8 per cent by weight of the said cycle stock, andthe said reaction product normally tending to form a haze in the oil;and a minor proportion, from about 0.001 per cent to about 0.3 per cent,suflicient to suppress the formation of said haze, of an oil-misciblemetal salt of a sulfonic acid.

5. A mineral oil composition comprising a. viscous mineral oil fractioncontaining a minor proportion, i'rom about 0.1 per cent to about 3.0 percent, sufllclent to inhibit the deteriorating efiects of oxidation uponthe oil, of a stable, oil-soluble, phosphorusand sulfur-containingreaction product obtained by reaction of phosphorus pentasulfide and acycle stock at about 150 C. for about 8 hours, said cycle stock beingcharacterized by an olefin content 01. about 6 per cent and an arcmaticcontent of about 4'. per cent, said phosphorus penta-sulfiderepresenting about 5 per cent by weight of the said cycle stock, and thesaid reaction product normally tending to form a haze in the oil; and aminor proportion, from about 0.001 per cent to about 0.3 per cent,sufiicient to suppress the formation of said haze, of an oil-misciblemetal salt oia sulfonic acid.

6. A mineral oil composition comprising a viscous mineral oil fractioncontaining a minor proportion, from about 0.1 per cent to about 3.0 percent, sufficient to inhibit the deteriorating effects of oxidation uponthe oil, of a stable, oil-soluble phosphorusand sulfur-containingreaction product obtained by reaction of phosphorus pentasulflde and ahydrocarbon stock at a temperature between about 125 C. and about 200 C.for a relatively short reaction time, said hydrocarbon stock beincharacterized by an olefinic content or from about 3 per cent to about'7 per cent and an aromatic content of from about per cent to about 60per cent, said phosphorus penta-sulfide representing from about 1 percent to about 8 per cent by weight of the said hydrocarbon stock, andthe said reaction product normally tending to form a haze in the oil;and a minor proportion, from about 0.001 per cent to about 0.3 per cent,suflicient to suppress the formation of said haze, of an oil-misciblemetal salt of an alkylsubstituted aromatic sulionic acid.

'7. A mineral oil composition comprising a viscous mineral oil fractioncontaining a minor proportion, from about 0.1 per cent to about 3.0 percent, sufficient to inhibit the deteriorating effects of oxidation uponthe oil, of a stable, oil-soluble, phosphorusand sulfur-containingreaction product obtained by reaction of phosphorus pentasulfide and ahydrocarbon stock at a temperature between about 125 C. and about 200 C.for a relatively short reaction time, said hydrocarbon stock beingcharacterized by an olefin content of from about 3 per cent to about 7per cent and an aromatic content of from about 40 per cent to about 60per cent, said phosphorus penta-sulfide representing from about 1 percent to about 8 per cent by weight of the said hydrocarbon stock, andthe said reaction product normally tending 10 to form a haze in the oil;and a minor proportion, from about 0.001 per cent to about 0.3 per cent,sufficient to suppress the formation of said haze, of an oil-misciblemetal salt oi an alkylsubstituted benzene sulfonic acid.

8. A mineral oil composition comprising a viscous mineral oil fractioncontaining a minor proportion, irom about 0.1 per cent to about 3.0 percent, sufficient to inhibit the deteriorating eflects of oxidation uponthe oil, of a stable, oil-soluble, phosphorusand sulfur-containingreaction product obtained by reaction of phosphorus pentasulfide and ahydrocarbon stock at a temperature between about C. and about 200 C. fora relatively short reaction time, said hydrocarbon being characterizedby an olefin content oi. from about 3 per cent to about 7 per cent andan aromatic content of from about 40 per cent to about 60 per cent, saidphosphorus penta-sulfide representing from about 1 per cent to about 8per cent by weight of the said hydrocarbon stock, and the said reactionproduct normally tending to form a haze in the oil; and a minorproportion, from about 0.001 per cent to about 0.3 per cent, sumcient tosuppress the formation of said haze, of an oil-miscible metal salt of awax-substiuted benzene sulfonic acid.

9. A mineral oil composition comprising a viscous mineral oil fractioncontaining a minor proportion, from about 0.1 per cent to about 3.0 percent, sufficient to inhibit the deteriorating eflects of oxidation uponthe oil, of a; stable, oil-soluble, phosphorusand sulfur-containingreaction product obtained by reaction of phosphorus pentasulfide and ahydrocarbon stock at a temperature between about 125 C. and about 200 C.for a relatively short reaction time, said hydrocarbon stock beingcharacterized by an olefin content of from about 3 per cent to about 7per cent and an aromatic content of from about 40 per cent to about 60per cent, said phosphorus pentasulfide representing from about 1 percent to about 8 per cent by weight or the said hydrocarbon stock, andthe said reaction product normally tending to form a haze in the oil;and a minor proportion, from about 0.001 per cent to about 0.3 per cent,suflicient to suppress the formation of said haze, of an oil-misciblebarium salt of diwax-substituted benzene sulfonic acid.

10. A mineral oil composition comprising a, viscous mineral oil fractioncontaining a minor proportion, from about 0.1 per cent to about 3.0 percent, suificient to inhibit the deteriorating effects of oxidation uponthe oil, of a stable, oil-soluble, phosphorusand sulfur-containingreaction product obtained by reaction of phosphorus-pentasulfide and ahydrocarbon stock at a temperature between about 125 C. and about 200 C.for a relatively short reaction time, said hydrocarbon stock beingcharacterized by an olefin content of from about 3 per cent to about '7per cent and an aromatic content of from about 40 per cent to about 60per cent, said phosphorus penta-sulfide representing from about 1 percent to about 8 per cent by weight of the said hydrocarbon stock, andthe said reaction product normally tending to form a haze in the oil;and a minor proportion, from about 0.001 per cent to about 0.3 per cent,suificient to suppress the formation of said haze, of an oil-misciblemetal salt of a petroleum sulfonic acid.

11. A mineral oil composition comprising a viscous mineral oil fractioncontaining a minor proportion, from about 0.1 per cent to about 3.0 percent, SLlffiCiBIiC to inhibit the deteriorating effects 1 l of oxidationupon the the oil, of a stable, oilsoluble, phosphorusandsulfur-containing reaction product obtained by reaction of phosphoruspenta-sulflde and a cycle stock at about 150 C. for about 8 hours, saidcycle stock being characterizeci by an olefin content of about 6 percent and an aromatic content of about 47 per cent, said phosphoruspenta-sulflde representing about 5 per cent by weight of the said cyclestock, and the said reaction product normally tending to torm a haze inthe oil; and a minor proportion, from about 0.001 per cent to about 0.3per cent, suflicient to suppress the formation of said haze, of anoil-miscible barium salt of diwax-substituted benzene sulfonic acid.

12. A mineral oil composition comprising a viscous mineral oil fractioncontaining a minor proportion, from about 0.1 per cent to about 3.0 percent, sufllcient to inhibit the deteriorating efl'ects of oxidation uponthe oil, of a stable, oil-soluble, phosphorusand sulfur-containingreaction product obtained by reaction of phosphorus penta-sulflde and acycle stock at about 150 C. for about 8 hours, said cycle stock beingcharacterized by an olefin content of about 6 per cent and an aromaticcontent of about 47 per cent, said phosphorus penta-sultide representingabout 5 per cent by weight or the said cycle stock, and the saidreaction product normally tending to form a haze in the oil; and a minorproportion, from about 0.001 per cent to about 0.3 per cent, sufilcientto suppress the formation of said haze, of an oil-miscible sodium saltof a petroleum sulf onic acid.

THOMAS T. NOLAND.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Number Name Date 2,136,391 Miller Nov. 15, 19382,202,394 Morway May 28, 1940 2,279,086 Bergstrom Apr. 7, 1942 2,315,529Kelso Apr. 6, 1943 2,316,082 Loane Apr. 6, 1943 2,342,572 Cook Feb. 22,1944 2,365,209 Musselman Dec. 19, 1944 2,373,094 Berger Apr. 10, 1945Certificate of Correction Patent No. 2,419,584.

April 29, 1947.

THOMAS T. NOLAND It is hereby certified that error appears in theprinted s numbered patent requiring correction as follows: Column 6,

test strike out the last do; and that the said Letters Patent ing CopperStrip ecification of the above able II, under the headshould be readwith this correction therein that the same may conform to the record ofthe case in the Patent Oifice.

Signed and sealed this 29th day of July, A. D. 1947.

LESLIE FRAZER,

First Assistant Oommiambner of Patents.

1 l of oxidation upon the the oil, of a stable, oilsoluble,phosphorusand sulfur-containing reaction product obtained by reaction ofphosphorus penta-sulflde and a cycle stock at about 150 C. for about 8hours, said cycle stock being characterizeci by an olefin content ofabout 6 per cent and an aromatic content of about 47 per cent, saidphosphorus penta-sulflde representing about 5 per cent by weight of thesaid cycle stock, and the said reaction product normally tending to torma haze in the oil; and a minor proportion, from about 0.001 per cent toabout 0.3 per cent, suflicient to suppress the formation of said haze,of an oil-miscible barium salt of diwax-substituted benzene sulfonicacid.

12. A mineral oil composition comprising a viscous mineral oil fractioncontaining a minor proportion, from about 0.1 per cent to about 3.0 percent, sufllcient to inhibit the deteriorating efl'ects of oxidation uponthe oil, of a stable, oil-soluble, phosphorusand sulfur-containingreaction product obtained by reaction of phosphorus penta-sulflde and acycle stock at about 150 C. for about 8 hours, said cycle stock beingcharacterized by an olefin content of about 6 per cent and an aromaticcontent of about 47 per cent, said phosphorus penta-sultide representingabout 5 per cent by weight or the said cycle stock, and the saidreaction product normally tending to form a haze in the oil; and a minorproportion, from about 0.001 per cent to about 0.3 per cent, sufilcientto suppress the formation of said haze, of an oil-miscible sodium saltof a petroleum sulf onic acid.

THOMAS T. NOLAND.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Number Name Date 2,136,391 Miller Nov. 15, 19382,202,394 Morway May 28, 1940 2,279,086 Bergstrom Apr. 7, 1942 2,315,529Kelso Apr. 6, 1943 2,316,082 Loane Apr. 6, 1943 2,342,572 Cook Feb. 22,1944 2,365,209 Musselman Dec. 19, 1944 2,373,094 Berger Apr. 10, 1945Certificate of Correction Patent No. 2,419,584.

April 29, 1947.

THOMAS T. NOLAND It is hereby certified that error appears in theprinted s numbered patent requiring correction as follows: Column 6,

test strike out the last do; and that the said Letters Patent ing CopperStrip ecification of the above able II, under the headshould be readwith this correction therein that the same may conform to the record ofthe case in the Patent Oifice.

Signed and sealed this 29th day of July, A. D. 1947.

LESLIE FRAZER,

First Assistant Oommiambner of Patents.

